WO2010115671A1 - Use of hollow bodies for producing water-absorbent polymer structures - Google Patents

Use of hollow bodies for producing water-absorbent polymer structures Download PDF

Info

Publication number
WO2010115671A1
WO2010115671A1 PCT/EP2010/052931 EP2010052931W WO2010115671A1 WO 2010115671 A1 WO2010115671 A1 WO 2010115671A1 EP 2010052931 W EP2010052931 W EP 2010052931W WO 2010115671 A1 WO2010115671 A1 WO 2010115671A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
polymer structure
absorbent polymer
particles
preferably
Prior art date
Application number
PCT/EP2010/052931
Other languages
German (de)
French (fr)
Inventor
Laurent Wattebled
Rainer Teni
Jörg HARREN
Original Assignee
Evonik Stockhausen Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DE102009016404A priority Critical patent/DE102009016404A1/en
Priority to DE102009016404.9 priority
Application filed by Evonik Stockhausen Gmbh filed Critical Evonik Stockhausen Gmbh
Publication of WO2010115671A1 publication Critical patent/WO2010115671A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/60Liquid-swellable gel-forming materials, e.g. super-absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10Esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • C08J3/128Polymer particles coated by inorganic and organic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/245Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/12Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2301/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08Cellulose derivatives
    • C08J2301/14Mixed esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Abstract

The present invention relates to water-absorbent polymer structures, at least partially containing hollow bodies having a shell made of an inorganic or organic material. The invention further relates to a method for producing water-absorbent polymer structures, to the water-absorbent polymer structures which can be obtained by said method, to a composite, to a method for producing a composite, to the composite which can be obtained by said method, to chemical products such as foams, moldings or fibers, to the use of water-absorbent polymer structures or a composite in chemical products, such as foams, moldings or fibers, and to the use of hollow bodies having a shell made of an inorganic or organic material.

Description

USE OF HOLLOW BODIES OF PRODUCING Water-Absorbing Polymer Structure

The present invention relates to water-absorbent polymer structure, to a process for producing water-absorbing polymer structure, obtainable by this method, water-absorbing polymer structure, a composite, a process for producing a composite, the composite obtainable by this process, chemical products such as foams, shaped articles or fibers, the use of water-absorbing polymeric formations or of a composite in chemical products, such as foams, molded articles or fibers, and the use of hollow bodies having a shell of an inorganic or organic material.

Superabsorbents are water-insoluble, crosslinked polymers which are able, under swelling and formation of hydrogels to absorb large amounts of aqueous liquids, in particular body fluids, preferably urine or blood, and of retaining them under pressure. In general, these amounts of liquids amount at least 10 times or even at least 100 times the dry weight of the superabsorbent or superabsorbent compositions of water. Because of these characteristic properties, these polymers are mainly used in sanitary articles such as baby diapers, incontinence products or sanitary napkins. A comprehensive overview of superabsorbers and superabsorbent compositions, their application fertil and their preparation is given by FL Buchholz and AT Graham (editors) in Modern Superabsorbent Polymer Technology ", Wiley-VCH, New York., 1998

The production of the superabsorbent is usually carried out by the radical polymerization carrying acid groups, mostly neutralized monomers in the overall genwart of crosslinkers. In this composition can be by selection of Monomerzu-, produce the crosslinkers and the polymerization conditions and the processing conditions for the hydro gel obtained after the polymerization polymers having different absorption properties. Other possibilities offered by the preparation of graft polymers, for example, using chemically modified starch, cellulose and polyvinyl alcohol according to DE-OS 26 12 846th

The current trend in diaper design is to produce even thinner constructions having a reduced cellulose fiber content and an increased proportion of superabsorbent. The advantage of thinner constructions is not only reflected in an improved wearing comfort, but also in reduced costs for packaging and warehousing. The trend toward ever thinner diaper constructions, the requirements profile has changed significantly to the superabsorbent. Of crucial importance now is the ability of the hydrogel to the fluid transmission and distribution. The greater amount of the hygiene article (amount of superabsorbent per unit area) in the polymer gequolle- NEN state may no barrier layer for subsequent liquid form (GeI blocking). the product has good transport properties, so an optimal utilization of the entire hygiene article can be guaranteed.

In addition to the permeability of the superabsorbent (given in the form of so-called Saline Flow Conductivity - SFC ") and the absorption capacity under a pressure load is in particular also the rate of absorption of the super-absorber particles (expressed in amount of liquid absorbed per gram of superabsorbent per second) a decisive criterion, which allows statements about whether a superabsorbent-containing this in large concentration of absorbent core which has only a small fluff, is capable, on its first contact with liquids, these beers to fast absorbers (so-called, ßrst aquisition "). This ßrst, aquisition "depends in absorbent cores having a high superabsorbent content among other things, the absorption rate of the superabsorbent material.

In order to improve the absorption rate of superabsorbent polymers, several approaches are known from the prior art. For example, the surface of the superabsorbent can be increased by using smaller superabsorbent particles are used with a correspondingly higher surface to volume ratio. This, however, has the permeability and other performance characteristics, such as the retention of the superabsorbent be reduced result. To avoid this problem, an increase in the surface of the superabsorbent particles can be achieved by preparing for example by pulverizing superabsorbent particles with irregular shapes even without reducing the particle diameter. It is also known for example from US 5,118,719 and US 5,145,713, to disperse the blowing agent in the monomer solution during polymerization, which release carbon dioxide when heated. The porosity of the resultant superabsorbent polymer provides more surface area in the polymer prepared, which ultimately enables an increased rate of absorption. US 5,399,391 is further known nachzuvernetzen such foamed superabsorbent particles at the surface to improve in this way the absorption capacity under a pressure load. The disadvantage of this approach, however, is that it is necessary due to the large surface of the foamed superabsorbent particles, the surface crosslinking agent as compared to non foamed superabsorbent particles to use in even larger quantities, which inevitably leads to an increased crosslinking density in the surface region. However, too high a crosslinking density of the surface areas resulting in a reduction of the absorption rate. Moreover, the use of blowing agents is disadvantageous, as the gas formed depends on the amount of monomer in the case of use of carbonates strongly on the temperature and the pH during the polymerization. In addition, blowing agents tend in the monomer solution to agglomerate into larger gas bubbles so that the it is difficult to control the final porosity of the superabsorbent material. The residence time in the monomer solution and in particular the exact time of the release of carbon dioxide are difficult to regulate in a use of carbonates.

The present invention was based on the object to overcome from the prior art disadvantages arising in connection with the production of water-absorbing polymer structures with high absorption rate.

In particular, the present invention had the object of providing wasserab- sorbent polymer structures which can be used in hygiene articles with high superabsorbent content very well. The water-absorbing polymers should in this case have in addition an advantageously high speed of absorption, a particularly high absorption under a pressure load, a particularly high retention and a very high permeability.

Also the present invention had the object of providing a process for producing water-absorbing polymeric formations with which it is possible to produce polymers having the above-described absorption characteristics in a well reproducible manner. Furthermore, the polymer particles obtained by this method after drying the polymer gel after carrying out a surface post should have a recognizable smaller decrease in the absorption rate than is the case with conventional water-absorbing polymeric formations.

- A - A contribution to solving the above-mentioned objects absorbing polymer structure at least partially comprising a hollow body with a shell of an inorganic or organic material.

Under the name of hollow body ", as used herein, preferably generally spherical structures are understood which have a shell of an inorganic or organic material which encloses a blowing agent. The term" blowing agents "are in the present invention preferably denotes compounds at atmospheric pressure and at a temperature in a range from -50 to 100 0 C, particularly preferably in a range of 0 to 50 0 C and most preferably in a range of 20 to 40 0 C, at least partially, and preferably are entirely gaseous. Such blowing agents include, for example, gases such as air or liquids, such as short-chain hydrocarbons.

According to a preferred embodiment of the water-absorbent polymer structure according to the invention, these include the hollow body in an amount in a range of 0.001 to 15 wt .-%, particularly preferably in a range of 0.01 to 7.5 wt .-%, and most preferably in a range of 0.1 to 3 wt .-%, each based on the total weight of the water-absorbent polymer structure according to the invention.

According to the invention, preferred water-absorbing polymer structures are fibers, foams or particles, fibers and particles being preferred and particles are sawn Sonders preferred.

According to Polymer fibers are sized so that they can be incorporated in or as yarns for textiles and also directly into textiles. It is preferable in the invention that the polymer fibers have a length in the range of 1 to 500 mm, preferably 2 to 500 mm and more preferably 5 to 100 mm and a diameter in the range of 1 to 200 denier, preferably from 3 to 100 denier and more preferably 5 have to 60 denier.

According to the invention, preferred polymer particles are sized so that they ERT 420.2-02 have an average particle size according to the range of 10 to 3000 microns, preferably 20 to 2000 microns and more preferably 150 to 850 microns. It is particularly preferred that the proportion of polymer particles having a particle size in a range of 300 to 600 .mu.m at least 30 wt .-%, particularly preferably at least 40 wt .-% and most preferably at least 50 wt .-%, based on the total weight of the water absorbing polymer particles is.

Furthermore, it is preferable in the invention that water-absorbent polymer structure according to the invention are based aufteilneutralisierter, crosslinking acrylic acid. In this connection passage, it is particularly preferable that water-absorbing polymeric formations of the present invention are crosslinked polyacrylates, which are at least 50 wt .-%, preferably at least 70 wt .-% and more preferably at least 90 wt .-%, each based on the weight-of the water-absorbent polymer structure consist of carboxylate groups-containing monomers. It is according to the invention further preferred that the polymer structures of the present invention, the water-based to at least 50 wt .-%, preferably at least 70 wt .-%, each based rylsäure on the weight of the water-absorbent polymer structure, to polymerized Ac-, preferably at least 20 is mol%, particularly preferably at least 50 mol% neutralized, and preferably in a range of 60 to 85 mol% beyond. As the inorganic materials that comprise the sheath of the hollow body, are, for example polycrystalline oxides, in particular polycrystalline aluminum oxide, in consideration, while the organic materials, in particular polymeric thermoplastic or non-thermoplastic materials are preferred.

A hollow body having a shell made of an organic material are preferably erfϊn- dung according hollow body selected from the group consisting understood:

- a hollow body having a shell made of a polymeric thermoplastic material;

Hollow body having a shell of a polymeric, non-thermoplastic material.

In general, can as a hollow body

based on thermoplastic or non-thermoplastic polymers, gas-filled microballoons (, gasfilled microballoons'), - polyelectrolyte multilayer capsules ( "polyelectrolyte multilayer capsules"), based on thermoplastic or non-thermoplastic polymers, so-called hollow spheres ( "hollow spheres") to Microsphere-based thermoplastic polymer particles as they are for example available under the trade designation "EXPANCEL ®", or

Hollow body having a shell made of polycrystalline alumina

be used. Under a hollow body having a shell of a polymeric thermoplastic material, preferably a hollow body is understood according to the invention, which is obtainable by a polymeric thermoplastic material which encloses a material that at a temperature increase its volume increased (= blowing agent) is heated. These hollow bodies therefore have a shell of a polymeric thermoplastic material, which encloses a propellant. As an example of such a polymeric thermoplastic material are for example those available from Akzo Nobel, Sundsvall, Sweden, under the trademark "Expancel ®" Microsphere particles called whose preparation is described, inter alia, in WO-A-2007/142593 . the blowing agent is preferably a compound whose boiling point is not higher than the melting or glass transition temperature of the polymeric thermoplastic material.

Such, enclosing a foaming agent, polymeric, thermoplastic materials may for example be obtained in that the monomers used for producing the polymeric thermoplastic polymer Siert in a suspension polymerization in the presence of a suitable propellant, for example, isobutane, and optionally in the presence of crosslinking agents, free-radically polymerized become. Such a process is described in detail, among others, in WO-A-2007 / 142,593th From the documents US 3,615,972, US 3,945,956, US 4,287,308, US 5,536,756, US 6,235,800, US 6,235,394, US 6,509,384, US-2004/0176486, US-2005/0079352, GB 1024195, EP-A-0486080, EP-AI 288 272, WO-A-2004/072160, JP-A-1987-286534, JP-A-2005-213379 are and JP-A-2005-272633 methods of making such materials are known. As the polymeric thermoplastic material in principle, all known to the skilled man, are polymeric thermoplastic materials, preferably a polymeric material is understood that plasma-up supply of heat can deform table wherein under a polymeric thermoplastic material erfϊndungsgemäß ". It is in this connection erfϊndungsgemäß especially preferred that the polymeric thermoplastic material is a by differential scanning calorimetry (DSC) specific melting or glass transition temperature in a range from 40 0 C to 240 0 C, particularly preferably from 60 0 C to 220 0 C and most preferably 80 to comprises 200 0 C.

Erfϊndungsgemäß suitable polymeric thermoplastic materials having the hollow bodies contained in the inventive water-absorbing polymeric formations as the sheath are, in particular polymers selected from the group consisting of poly (meth) acrylates, (meth) acrylic acid copolymers, game as examples ethylene- (meth ) acrylic acid copolymers, (meth) acrylic acid ester copolymers, maleic acid copolymers, for example, maleic-propylene copolymers, polyurethanes, vinyl acetate copolymers, for example, an ethylene len-vinyl acetate copolymer or vinyl acetate-butyl acrylate copolymers, styrene polymers rol copolymers , for example, butyl acrylate-styrene copolymers, and polyvinyl alcohols Polycarbona- th. Erfϊndungsgemäß are particularly suitable

Hollow body, the polymeric thermoplastic material is based on acrylonitrile and vinyl ethers such as those described in WO-A-2007/142593, wherein as vinyl ethers, in particular vinyl ether selected from the group consisting of methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether,

Isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, sec-butyl vinyl ether, and mixtures thereof can be used, wherein the copolymers of acrylonitrile and vinyl ether acrylate, optionally also through the use of crosslinking agents such as divinyl benzene, ethylene glycol di (meth) or other , in WO-A 2007/142593 crosslinkers mentioned, may be crosslinked;

Hollow body, the polymeric thermoplastic material is based on acrylonitrile, methacrylonitrile, acrylic acid esters and methacrylic acid esters, such as those described in WO-A-2007/091961 or in WO-A-2007/091960, wherein also these polymers optionally through the use of in WO-A-2007/091961 or crosslinking agents described in WO-A-2007/091960 may be crosslinked.

Hollow body, the polymeric thermoplastic material is based on polyvinyl idenchlorid, such as the products available under the trade designation EXPANCEL ® by the company Akzo Nobel.

In the hollow bodies to the shell of the polymeric thermoplastic material, a blowing agent is preferably included, which at atmospheric pressure and at a temperature in a range from -50 to 100 0 C, particularly preferably in a range of 0 to 50 0 C, and most preferably at least partly present as a gas in a range of 20 to 40 0 C. In this blowing agent is preferably a hydrocarbon, for example a hydrocarbon selected from the group consisting of methane, ethane, propane, n-butane, iso-butane, n-pentane, iso-pentane, neo-pentane, cyclopentane, hexane, iso-hexane, neo-hexane, cyclohexane, heptane, iso-heptane, octane, iso-octane and iso-dodecane to petroleum ether, or halogenated hydrocarbons, game as examples halogenated hydrocarbons selected from the group consisting of methyl chloride, methylene chloride, dichloroethane, dichloroethylene, trichloroethane rethane, trichlorethylene, trichlorofluoromethane and perfluorinated hydrocarbons such as fluorine contained ether. Water can also serve as a propellant. The boiling point of the propellant at atmospheric pressure is preferably in the range from -50 to 100 0 C, particularly preferably 0 to 50 0 C, and most preferably 20 to 40 0 C. conceivable, however, in principle, the use of hollow bodies having a shell of a polymeric thermoplastic material, which are filled with air.

In addition to the above-described hollow bodies, so-called gas-filled microballoons can (in the literature as gas-filled micro-balloons "hereinafter), polyelectrolyte multilayer capsules (in the literature as" polyelectrolyte multilayer capsules "hereinafter) or (with gaseous or liquid Verbindun- gen-filled hollow spheres in the literature referred to as "hollow spheres") are used, wherein the microballoons and the hollow spheres can be based on thermoplastic polymers as well as non-thermoplastic polymers as a shell material.

Examples of gas-filled micro-balloons are about microballoons, which consist of a shell of a crosslinked polyvinyl alcohol. Such microballoons are described in Cavalieri et al, ^ table Polymeric microballoons as multi-functional device for Biomedical Uses: described Synthesis and Characterization " ', Langmuir 2005, pages 8758-8764 (21 (19) vol.) As an example of appropriate. polyelectrolyte multilayer capsules may be mentioned those capsules in Heuvingh et al., JSaIt softening of polyelectrolyte multilayer capsules ", Langmuir, 2005 (Vol. 21 (7)), pages 3165-3171 will be described. Examples of novel suitable hollow spheres are, for example, sold by Rohm & Haas, France, under the name ROPAQUE ®, for example ROPAQUE ® ULTRA E Opaque Polymer and described in EP-AI 757 639 products. In these products, a liquid (water) is enclosed by a polymer sheath, which can pass through the polymer membrane during the evaporation of the liquid, so that remains an air-filled hollow body. As an example of a hollow body having a shell made of an inorganic material are used as, ßubble Alumina designated "and under the designations GL ®, GLHP ® or Duralum ® AB from the company Rio Tinto Alcan, France, distributed, called on polycrystalline alumina-based particles ,

According to a preferred embodiment of the invention, water-absorbent polymer structure a part of the hollow body absorbing polymer structures is at least formed as a matrix in which is embedded, it being particularly preferred that the hollow body are evenly distributed in the water-absorbing polymeric formations.

Such a structure is obtainable, for example, that the hollow body with a shell of the inorganic or organic material of the monomer solution, which was used to prepare the water-absorbent polymer structure, before or during the polymerization is added, or in which after the polymerization polymer gel obtained is incorporated, wherein in the case of the use of a hollow body ex- pandiert with a casing made of a polymethyl reindeer, thermoplastic material, this hollow body before their use or may be used in not expanded condition. The water-absorbent polymer structure according to the invention are therefore preferably obtainable by a process comprising the process steps:

i) radical polymerization of an aqueous monomer solution comprising a polymerizable, monoethylenically unsaturated, a Säuregruppe- bearing monomer (αl) or a salt thereof, optionally one (with the monomer αl) polymerizable monoethylenically unsaturated monomer (α2), and optionally a crosslinker (α3 ) to obtain a polymer gel; ii) optionally, comminuting the hydrogel; iii) drying the optionally comminuted hydrogel to obtain water-absorbing polymeric particles; iv) optionally grinding and sieving the thus obtained wasserabsorbie- leaders polymer particles; v) optionally, further surface modification of the thus obtained water-absorbing polymer particles;

wherein at least one of the conditions I) and II), optionally also both conditions I) and II) is satisfied, or are:

I), the hollow body having a shell of the inorganic or organic material can be added to the monomers in process step i);

II) the hollow body having a shell of the inorganic or organic material can be obtained in the hydrogel in method step i) or incorporated in the product obtained in method step ii), comminuted hydrogel.

In method step i) an aqueous monomer solution is initially including a polymerizable, monoethylenically unsaturated, a Säuregruppe- bearing monomer (αl) or a salt thereof, optionally one (with the monomer αl) polymerizable monoethylenically unsaturated monomer (α2), and optionally a crosslinking agent (α3) free-radical polymerization to obtain a polymer gel. The monoethylenically unsaturated, acid groups-bearing monomers (αl) can be partially or fully, preferably partially neutralized. Preferably, the monoethylenically unsaturated, acid groups-bearing monomers (αl) at least 25 mol%, particularly preferably at least 50 mol%, and preferably neutralized in addition to 50-80 mol%. In this connection, reference is made to DE 195 29 348 Al, the disclosure of which is hereby incorporated by reference. The neutralization may be partly or completely after the polymerization. Furthermore, the neutralization may limetallhydroxiden with alkali, alkaline earth done, ammonia and carbonates and bicarbonates. In addition, any further base is conceivable which forms a water soluble salt with the acid. A mixed neutralization with different bases is also conceivable. Preferably, the neutralization with ammonia, and alkali metal hydroxides is, more preferably with sodium hydroxide and with ammonia.

Further, the free acid groups can predominate in the inventive water-absorbing polymeric formations, so that this polymer structure has a region in the acidic pH. This acidic water-polymer structures can be formed by polymer structures with free basic groups, preferably amine groups, which is basic compared to the acidic polymer structure, are at least partially neutralized. These polymer structures are referred to in the literature as, JMixed-Bed Ion-Exchange Absorbent Polymers "(MBIEA polymers), and are, inter alia, in WO 99/34843 Al discloses. The disclosure of WO 99/34843 Al is hereby incorporated by reference and is thus regarded as part of the disclosure. in general MBIEA polymers represent a composition to a basic polymer structure, which are capable of exchanging anions, and on the other hand an acid in comparison to the basic polymer structure polymer structure that is capable of exchanging cations. the basic polymer structure has basic groups and is typically obtained by the polymerization of monomers containing basic groups or groups which can be converted into basic groups. these monomers are especially those which primary, secondary or tertiary amines or the corresponding phosphines or at least two of the above funktionel have len groups. This group of monomers, in particular ethylene amine, allylamine, Dially- include lamin, 4-aminobutene, Alkyloxycycline, vinylformamide, 5-aminopentene, carbo- diimide, formaldacine, melamine and the like, as well as their secondary or tertiary amine derivatives.

Preferred monoethylenically unsaturated, acid groups-bearing monomers (αl) are preferably those compounds in WO 2004/037903 A2, which is hereby incorporated by reference and thus forms part of the disclosure, referred to as ethylenically unsaturated, acid group-containing monomers (αl) , Particularly preferred monoethylenically unsaturated, acid groups-bearing monomers (αl) are acrylic acid and methacrylic acid, with acrylic acid being most preferred.

As with the monomers (αl) copolymerizable, monoethylenically unsaturated monomer (α2) can acrylamides, methacrylamides or vinyl amides are used. Other preferred co-monomers are in particular those in the -carrying monomers (αl) are preferably those compounds which are mentioned in WO 2004/037903 A2 as co-monomers (α2)

As a crosslinking agent (α3) are also preferably used those compounds which are mentioned in WO 2004/037903 A2 as crosslinkers (α3). Among these crosslinking agents, water-soluble crosslinkers are particularly preferred. Most preferred are N, N 'methylenebisacrylamide, polyethylene glycol di (meth) acrylates, triallylmethylammonium chloride, tetraallylammonium chloride and with 9 moles of ethylene oxide per mole of acrylic acid produced lenglykolacrylat Allylnonaethy-.

In addition to the monomers (αl), and optionally (α2) and optionally the crosslinking agent (α3) may also include water soluble polymers (α4) the monomer solution. Preferred water-soluble polymers comprising partially or fully hydrolyzed polyvinyl alcohol, polyvinylpyrrolidone, starch or starch derivatives, polyglycols or polyacrylic acid. The molecular weight of these polymers is not critical as long as they are water soluble. Preferred water-soluble polymers are starch or starch derivatives or polyvinyl alcohol. The water-soluble polymers, preferably synthetic, such as polyvinyl alcohol, can not only serve as grafting base for the monomers to be polymerized. It is also feasible to mix these water-soluble polymers after the polymerization, with the polymer gel or the already dried, water-absorbing polymer gel.

Furthermore, the monomer solution may also contain adjuvants (α5), wherein to these particular tools that may be necessary for polymerization initiators or complexing agents such as EDTA belong.

Suitable solvents for the monomer organic solvents or mixtures are water, from water and organic solvents tracht in loading, the choice of the solvent depends in particular on the manner of polymerization.

The relative amount of monomers (αl) and (α2) as well as crosslinking agents (α3) and water soluble polymers (α4) and auxiliary (α5) in the monomer (OH ne consideration of the polymeric material having a hollow body) is preferably chosen so that the water-absorbent polymer structure obtained in step iii) after drying

20 to 99.999 weight .-%, preferably from 55 to 98.99 wt .-% and particularly preferably 70 to 98.79 wt .-% of the monomers (αl), 0 to 80 wt .-%, preferably to 0 to 44.99 wt .-% and particularly preferably from 0.1 to 44.89 wt .-% of the monomers (α2), 0 to 5 wt .-%, preferably from 0.001 to 3 wt .-% and particularly preferably 0.01 to 2.5 wt .-% of the crosslinking agents (α3) by weight in 0 to 30 wt .-%, preferably 0 to 5 wt .-% and particularly preferably from 0.1 to 5 .-% of the water-soluble polymers (α4), 0 to 20 wt .-%, preferably 0 to 10 wt .-% and particularly preferably 0.1 to 8 wt .-% to the tools (α5), and - 0.5 to 25 wt .-%, preferably 1 to 10 wt .-% and particularly preferably 3 to 7 wt .-% water (α6)

based, with the sum of the weight amounts (αl) to (α6) wt .-% 100. Optimum values ​​for the concentration of in particular the monomers, crosslinking zer and water-soluble polymers in the monomer can be determined by simple preliminary tests, or also to the prior art, in particular the publications US 4,286,082, DE-A-27 06 135, US 4,076,663, DE A-35 03 458, DE 40 20 780 Cl, DE-A-42 44 548, DE-A-43 33 056 and removed DE-A-44 18 818th Radical polymerization of the monomer, all known to those skilled polymerization process can basically be considered. For example, in this regard, bulk polymerization, which preferably takes place in kneading reactors such as extruders, solution polymerization, spray polymerization, inverse emulsion polymerization and inverse suspension polymerization.

solution polymerization is preferably carried out in water as solvent. The solution may be continuous or discontinuous. From the prior art, a wide range of possible variations with respect to reaction conditions such as temperatures, type and amount of initiators and the reaction solution is apparent. Typical processes are described in the following patents: US 4,286,082, DE-A 27 06 135 Al, US 4,076,663, DE-A-35 03 458, DE 40 20 780 C 1, D EA 42 44 548 DE-A- 43 33 056, DE-A-44 18 818. the disclosures of which are hereby incorporated by reference and thus part of the disclosure. The polymerization is generally customary manner, by an initiator. As initiators for initiating polymerization can all be used under the polymerization free radical-forming initiators are used which are usually in the production of superabsorbents. An initiation of the polymerization by the action of electron beams on the polymerizable aqueous mixture is also possible. However, the polymerization can advertising initiated in the absence of initiators of the abovementioned type by the action of high energy radiation in the presence of the photoinitiators. Polymerization initiators may be dissolved in the monomer or dis- persed. Possible initiators are all occur to those skilled known disintegrate into free radicals compounds. These include in particular those initiators which have already been mentioned in WO-A-2004/037903 as possible initiators. a redox system consisting of hydrogen peroxide used, sodium peroxodisulfate and ascorbic acid for the preparation of the sorbent wasserab- polymer structure.

Inverse suspension and emulsion polymerization can be used to prepare the water-absorbing polymer structure. According to these processes, an aqueous, partly neutralized solution of monomers (αl) and (α2), optionally containing the water-soluble polymers (α4) and auxiliary (α5), by means of protective colloids and / or emulsifiers factors in a hydrophobic dispersed organic solvent and the polymerization is started by radical initiators. The crosslinking agents (α3) are either dissolved in the monomer solution and metered together with or separately and optionally added during the polymerization. Optionally, the addition of a water soluble polymer (α4) is carried out as the graft base via the monomer solution or by directly placing in the oil phase. Subsequently the water is azeotropically removed from the mixture and abfütriert the polymer.

Furthermore, the cross-linking occur by polymerization tion of dissolved in the monomer polyfunctional crosslinking agent (α3) and / or by reacting suitable crosslinking agents with functional groups of the polymer during the polymerization both in solution and in the inverse suspension and emulsion polymerization. The methods are, for example, in the publications US 4,340,706, DE-A-37 13 601, DE-A 28 40 010 describes and WO-A-96/05234, whose relevant disclosure is incorporated herein by reference.

In process step ii), the polymer gel obtained in process step i) is optionally comminuted, this comminution being carried out in particular when the polymerization is carried out by means of a solution polymerization. Crushing, by art-known crushing devices such as a meat grinder, take place.

In process step iii) the optionally previously comminuted polymer gel is dried. The drying of the polymer gel is preferably done in suitable dryers or ovens. Examples include rotary kilns, fluidized bed dryers, plate dryers, paddle dryers or infrared dryers. Furthermore, it is preferable in the invention that the drying of the polymer gel in process step iii) wt .-% is effected to a water content of 0.5 to 25 wt .-%, preferably from 1 to 10, wherein the drying temperatures are usually in a range of 100 There are up to 200 0 C.

In step iv) the polymer structure obtained in process step iii), the water can in particular if they were obtained by Lösungspo- lymerisation, be ground and sieved to the above-mentioned desired particle size. Grinding of the dried water-absorbing polymeric formations is preferably carried out in suitable mechanical comminution devices such as a ball mill, during the screening can be done for example, by using sieves with a suitable mesh size.

In method step v) the optionally ground and sieved water-absorbent polymer structures are surface-modified, said surface modification preferably comprises a surface postcrosslinking.

For the surface the dried and optionally ground and sieved water-absorbent polymer structure from step iii) or iv) but not yet dried, but already comminuted polymer gel from step ii) is brought into contact with a preferably organic, chemical surface. Here, the post-crosslinking agent is in particular if it is below the post-crosslinking not liquid, preferably in form of a fluid brought comprising the post-crosslinker and a solvent with the wasserabsorbie- leaders polymer structures or the polymer gel in contact. As solvent, preferably water, used water-miscible organic solvent such as methanol, ethanol, 1-propanol, 2-propanol or 1-butanol or mixtures of at least two of these solvents, with water being the preferred solvent most. Furthermore, it is preferable that the post-crosslinking agent in the fluid in an amount in a range of 5 to 75 wt .-%, particularly preferably 10 to 50 wt .-% and most preferably 15 to 40 wt .-%, based on the total weight of the fluid is contained. The contacting of the water-absorbent polymer structure or of the optionally comminuted polymer gel with the fluid containing the renegotiations crosslinker is preferably carried out by thorough mixing of the fluid with the polymer structure and the polymer gel.

Suitable mixing units for applying the fluid are, for. As the Patterson-Kelley mixers, DRAIS turbulence mixers, Lödige mixers, Ruberg mixers, screw mixers, pan mixers and fluid-bed mixers, as well as continuously operated vertical mixers wherein the polymer structure is mixed at a rapid frequency using rotating knives (Schugi mixer).

The polymer structures or the polymer gel is preferably used at the post-crosslinking with a maximum of 20 -.%, Particularly preferably at most 15 wt .-%, preferably in addition with a maximum of 10 -.%, Further still more preferably at most 5. brought% of solvent, preferably water -.

In polymer structures in the form of preferably spherical particles, it is erfmdungsgemäß further preferred that the bringing into contact is carried out such that only the outer region, but not the inner region of the particulate polymer formation with the fluid, and thus the post-crosslinking agent are brought into contact.

As postcrosslinkers are meant compounds preferably having Any artwork least two functional groups which can react with functional groups of a polymer structure in a condensation reaction (= condensation), in an addition reaction or a ring opening reaction. As post, those are preferred that have been mentioned as crosslinkers of crosslinker II in WO-A-2004 / 037,903th Among these compounds, particularly preferred as postcrosslinkers condensate sationsvernetzer such as diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, polyglycerol, propylene glycol, diethanolamine, triethanolamine min, polyoxypropylene, oxyethylene-oxypropylene block copolymers, sorbitan fatty acid ester, polyoxyethylene sorbitan, trimethylolpropane, pentaerythritol , polyvinyl alcohol, sorbitol, l, 3-dioxolan-2-one (ethylene carbonate), 4-methyl-l, 3- dioxolan-2-one (propylene carbonate), 4,5-dimethyl-l, 3-dioxolan-2-one , 4,4-dimethyl-l, 3-dioxolan-2-one, 4-ethyl-l, 3-dioxolan-2-one, 4-hydroxymethyl-l, 3-dioxolan-2-one, l, 3-dioxane -2-one, 4-methyl-l, 3-dioxan-2-one, 4,6-dimethyl-l, 3-dioxan-2-one and l, 3-dioxolan-2-one.

After the polymer structures or the polymer gels comprising the post are brought into contact with the post-crosslinking agent or with the fluid, the advertising them to a temperature in the range of 50 to 300 0 C, preferably 75 to 275 ° C and more preferably 150 to 250 0 C heated so that, preferably whereby the outer region of the polymer structures in comparison to the inner region more highly crosslinked (= post-crosslinking) and, if polymer are used, they are at the same time dried. The duration of the heat treatment is limited by the risk that the desired property profile of the polymer structure is destroyed as a result of the action of heat.

Further, the surface modification in method step v) the treatment with a compound containing aluminum, preferably Al 3+ - ions include, whereby it is preferred that this treatment is performed simultaneously with the surface postcrosslinking by a preferably wässri- ge solution comprising the post-crosslinked as well as the compound comprising aluminum, preferably Al 3+ ions is contacted with the water-absorbing polymeric formations in contact and then heated. It is preferred that the compound containing aluminum in an amount preferably in a range of 0.01 to 30 wt .-%, particularly preferably in an amount in a range of 0.1 to 20 wt .-% and moreover in an amount in a range of 0.3 to 5 wt .-%, each based on the weight of the water-absorbent polymer structure is brought into contact with the water-absorbing polymeric formations.

Preferred aluminum-containing compounds are water-soluble connects fertilize containing Al 3+ ions, such as AlCl 3 .6H 2 O, NaAl (SO 4) 2 x 12 H 2 O, KA1 (SO4) 2 x 12 H 2 O or Al 2 (SO4) 3 x 14-18 H2 O, aluminum lactate or water-insoluble aluminum compounds such as aluminum oxides, such as Al 2 O 3, or aluminates. Particularly preferred are mixtures of aluminum lactate and aluminum sulfate are used.

It is now preferred in the invention that at least one of the conditions I) and II), optionally also both conditions I) and II) is satisfied, or are:

I), the hollow body having a shell of the inorganic or organic material can be added to the monomers in process step i);

II) the hollow body having a shell of the inorganic or organic material can be obtained in the hydrogel in method step i) or incorporated in the product obtained in method step ii), comminuted hydrogel.

In the case of the use of hollow bodies having a shell of a polymeric thermoplastic material it is conceivable in principle, according to alternative I) or II) already expanded polymeric employ thermoplastic materials or polymeric, thermoplastic materials, which are not expanded ( that is, those in which the present example, in the case of the use of hydrocarbons as blowing agent, the blowing agent still in liquid form), but which expand by the heat generation during polymerization, by the heat supply during the drying or by the heat supply during the surface postcrosslinking.

According to a particular embodiment of the process, with the polymer structure according to the invention, water can be obtained, and in which hollow bodies are used with a sheath of a polymeric thermoplastic material, the hollow body used in accordance with the alternatives I) and II) are in the form of particles, having an average volume Vi and 2> Vi can be expanded by increasing the temperature to the average volume V, this expansion preferably during at least one of process steps i) is carried out to v). In connection with such particulate, unexpanded polymeric, thermoplastic materials, it is particularly preferred that at least 50 wt .-% of these particles, even more preferably at least 75 wt .-% of these particles, and most preferably at least 90 wt .-% these particles particularly preferably more preferably have a particle size in a range of 0.01 to 60 microns, in a range of 1 to 50 microns and in a range of 5 to 40 microns.

As examples of such, not yet expanded polymeric thermoplastic materials include for example those sold by Akzo Nobel Expancel ® 551 DU 20, Expancel ® 551 DU 40, Expancel ® 461 DU 20, Expancel ® 461 DU 40, Expancel ® 051 DU 40, EXPANCEL ® 053 DU 40, EXPANCEL ® 009 DU 80, EXPANCEL ® 091 DU 80, EXPANCEL ® 091 DU 140, EXPANCEL ® 092 DU 80, EXPANCEL ® 092 DU 140, EXPANCEL ® 093 DU 120, EXPANCEL ® 920 DU 40 , EXPANCEL ® 930 DU 120, EXPANCEL ® 950 DU 80, EXPANCEL ® 950 DU 120, EXPANCEL ® 642 WU 40, EXPANCEL ® 551 WU 20, EXPANCEL ® 551 WU 40, EXPANCEL ® 551 WU 80, EXPANCEL ® 461 WU 20, EXPANCEL ® called 461 WU 40, EXPANCEL ® 051 WU 40, EXPANCEL ® 007 WU 40, EXPANCEL ® 053 WU 40, EXPANCEL ® 054 WUF 40, EXPANCEL ® 091 WU 80 and EXPANCEL ® 920 WUF 40th Such particulate polymeric thermoplastic materials preferably comprise an at least partially still present in liquid form blowing agent, such as a still present in liquid form hydrocarbon, which is surrounded by a sheath of a polymeric thermoplastic material and which at least partially evaporates when heated, and so the causing expansion of the polymeric thermoplastic material to form a hollow body.

Furthermore, it is preferable in the invention that the enclosing an unexpanded blowing agent, polymeric, thermoplastic materials usually a temperature Tstart (this is the temperature at which the expansion of the propellant surrounding polymeric, thermoplastic material begins) in a range of 40 to 180 0 C, particularly preferably in a range of 60 to 160 0 C and most preferably in a range of 70 to 150 0 C, while the temperature T max (this is the temperature, in which reaches the maximum expansion) is preferably is in a range of in a range from 100 to 240 0 C, particularly preferably in a range from 120 to 220 0 C and most preferably in the range 140-210 0 C.

According to another particular embodiment of the process, with the polymer structure of the present invention, the water are available and are employed al wherein the hollow body having a shell made of a polymeric thermoplastic Materi-, the hollow body used in accordance with the alternatives I) and II) are in the form of particles before, which have an average volume V 2 and which are obtainable in that the particles have been based on a mean volume Vi <V 2 expanded to the mean volume V2. In connection with those already expanded, when in use, polymethyl reindeer, thermoplastic materials, it is preferable that, still more preferably at least 50 wt .-% of these particles is at least 75 wt .-% of these particles, and most preferably than 90. -% of these particles have a particle size in a range of 20 to 100 microns and more preferably in a range of 30 to 60 microns.

Examples of such already expanded, particulate, polymeric, thermoplastic materials may be mentioned for example the products Expancel ® WE and Expancel ® DE available from Akzo Nobel. Such polymeric, thermoplastic materials preferably comprise an at least partially vorliegendes already in gaseous blowing agent, such as an at least partially already gaseous present hydrocarbon, which is surrounded by a sheath of a polymeric thermoplastic material.

According to another particular embodiment of the method with which the inventive water-absorbing polymer structures are available and are used in the hollow body with a shell of a polymeric, non-thermoplastic material, are these polymers, non-thermoplastic Mate also rials preferably in the form of spherical particles before, it is preferred that at least 50 wt .-% of these particles, even more preferably at least 75 wt .-% of these particles, and most preferably at least 90 wt .-% of these particles have a diameter in a range of 10 nm to 100 microns, more preferably in a range of 25 nm to 50 microns and most preferably in a range of 50 nm to 30 microns.

If the hollow bodies are added to a shell of the inorganic or organic material according to alternative I) of the monomer solution, so it can be stirred directly into the monomer solution. However, it is also conceivable that, to disperse initially in a small volume of a solvent such as water and then to add this dispersion to the monomer. Hollow bodies such as the ROPAQUE ® available from Rohm & Haas - Products are already available as an emulsion and the monomer may possibly already be added in the form of emulsion. If the hollow body incorporated with a shell of the inorganic or organic material according to alternative II) in the hydrogel or the comminuted hydrogel, these hollow bodies are incorporated immediately or after predispersion in a solvent, for example water by means of suitable kneading in the gel.

According to a particular embodiment of the invention, water-absorbent polymer structure, these one described herein in accordance with the de Testmetho b ertain absorption rate of at least 0.30 g / g / sec, even more preferably of at least 0.35 g / g / sec and most preferably from at least 0.40 g / g / sec, preferably an absorption speed of 1, 0 g / g / sec and even more preferably from 0.6 g / g / sec is not exceeded.

Moreover, it is erfmdungsgemäß preferred that the water-absorbing polymeric formations comprise at least one of the following properties:

(SSL) an described herein in accordance with the test method specified absorption under a pressure of 50 g / cm 2 of at least 22.0 g / g, preferably of at least 23.5 g / g and most preferably from 24 g / g, preferably a value of 28 g / g, even more preferably from 27 g / g and most preferably from 26 / g is preferably not exceed g;

(SS2) according to the herein described a test method specified retention of at least 26 g / g, preferably of at least 26.5 g / g and most preferably from 27 g / g, preferably a value of 36 g / g, even more preferably is from 34 g / g and most preferably from 32 g / g not exceeded;

(SS3) a test method described herein certain permeability of at least 45 x 10 -7 cm 3 sec / g, preferably of at least 75 x 10 "7 cm 3 sec / g and most preferably of at least 100 x 10" 7 cm 3 sec / g and preferably a value of 19O x 10 "7 cm 3 sec / g, even more preferably from 170 x 10" 7 cm 3 sec / g, and most preferably from 15O x 10 "7 cm 3 sec / g not exceeded becomes.

According to the invention particular preferred, water-absorbing polymer structures are those which preferably in addition to the above-described advantageous rate of absorption following properties or property combinations: (SSL), (SS2), (SS3), (SSL) (SS2), (SSL) (SS3 ), (SS2) (SS3), (ßiχp2) (SS3).

A contribution towards achieving the abovementioned objects is still a

A process for producing water-absorbing polymeric formations, comprising the

Steps:

i) radical polymerization of an aqueous monomer solution comprising a polymerizable, monoethylenically unsaturated, a Säuregruppe- bearing monomer (αl) or a salt thereof, optionally one (with the monomer αl) polymerizable monoethylenically unsaturated monomer (α.2), and optionally a crosslinking agent (α3) to obtain a polymer gel; ii) optionally, comminuting the hydrogel; iii) drying the optionally comminuted hydrogel to obtain water-absorbing polymeric particles; iv) optionally grinding and sieving the thus obtained water-absorbing polymer particles; v) optionally, further surface modification of the thus obtained water-absorbing polymer particles;

wherein at least one of the conditions I) and II), optionally also both conditions I) and II) is satisfied, or are:

I) hollow bodies are added to the monomers in process step i) material including a shell of an inorganic or organic ma-;

II) a hollow body with a shell of an inorganic or organic material may be incorporated in the product obtained in process step i) or in the hydrogel obtained in step ii), comminuted hydrogel.

With respect to the method steps i) to v) and of the alternatives (I) and (II), reference is made to the interpretive statements in conjunction with the erfmdungsgemä- SEN, water-absorbing polymer structure.

Also in connection with the inventive method for producing water-absorbing polymeric formations it is therefore conceivable in the case of the use of hollow bodies having a shell of a polymeric thermoplastic material, according to alternative I) or II) already expanded polymeric employ thermoplastic materials or even non-expanded polymeric thermoplastic materials.

According to a preferred embodiment of the method according to the invention, be employed in the hollow body having a shell made of a polymeric thermoplastic material, the hollow body used in accordance with the alternatives I) and II) are in the form of particles which sen an average volume Vi aufwei- and 2> Vi can be expanded by increasing the temperature to the average volume V, this expansion preferably during at least one of process steps i) is carried out to v). With regard to the preferred particle size does not already expanded materials as well as in terms of concrete examples of suitable materials, reference is made to the above statements relating to the invention, water-absorbing materials.

According to another particular embodiment of the inventive encryption driving, be used in the hollow body having a shell made of a polymeric thermoplastic material, the hollow body used in accordance with the alternatives I) and II) are in the form of particles which have an average volume V 2 have and which are obtainable in that the particles WOR starting from a mean volume Vi <V 2 expanded to the average volume V 2 are the. Here, too, reference is made to the above statements relating to the invention, water-absorbing materials in terms of the preferred particle size of such already expanded materials as well as in terms of specific examples of suitable materials.

Furthermore, it is preferred that the hollow body having a shell of an inorganic or organic material in an amount in a range of 0.001 to 15 wt .-%, particularly preferably in a range of 0.01 to 7.5 wt .-% and most preferably are employed in a range of 0.1 to 3 wt .-%.

A contribution to achieving the abovementioned objects is also obtainable by the method described above, the water-absorbing polymer structures. A further contribution to achieving the objects described above is a composite comprising water-absorbing polymer structures according to the invention or obtainable by the inventive process absorbing polymer structures and a substrate. It is preferred that the polymer structures of the invention and the substrate are firmly connected to each other. As substrates are films of polymers such as preferably for example, from polyethylene, polypropylene or polyamide, metals, non-woven, fluff, tissues, tissues, natural or synthetic fibers, or other foams. Furthermore, it is preferable in the invention that the composite comprises at least one region which water-absorbing polymeric formations according to the invention in an amount in the range of about 15 to 100 wt .-%, preferably about 30 to 100 wt .-%, more preferably from about 50 to 99.99 wt .-%, further preferably from about 60 to 99.99 wt .-% and more preferably from about 70 to 99 wt .-%, each based on the total weight of the relevant region of the composite, whereby this region preferably has a size of at least 0.01 cm, preferably at least 0.1 cm, and most preferably at least 0.5 cm 3.

In a particularly preferred embodiment of the invention comparison nationwide is a sheet-like composite as "absorbent material" in WO-A- 02/056812 as described. The disclosure of WO-A-02/056812, especially as regards the detailed structure of the composite, of the area of ​​its components, and its thickness is hereby incorporated by reference and is part of the disclosure of the present Erfϊn-

A further contribution to solving above-mentioned objects provides a method of producing a composite, wherein the water-absorbing polymeric formations according to the invention or obtainable by the process of this invention water-absorbent polymer structure and a substrate and optionally an additive are brought into contact with each other. As substrates, those substrates are preferably used that have already been mentioned in connection with the inventive composite.

A contribution to achieving the abovementioned objects is also a composite obtainable by the method described above, this composite is preferably the same properties as the above-described composite of the present invention.

A further contribution to solving above-mentioned objects chemical products comprising the polymer structures of the invention or a composite according to the invention. Preferred chemical products include foams, formed bodies, fibers, sheets, films, cables, sealing materials, liquid-absorbing hygiene articles, especially diapers and sanitary napkins, carriers for plant and fungus growth-regulating agents or plant-zenschutzwirkstoffe, additives for building materials, packaging materials and soil additives.

Also, the use of the polymer structures according to the invention or of the composite according to the invention in chemical products, preferably in the above-mentioned chemical products, especially in hygiene articles such as diapers or sanitary napkins, and to the use of the superabsorbent particles as a carrier for plant or fungus growth-regulating agents or plant protection active ingredients make a contribution to solve the above-mentioned objects. When used as carriers for plant or fungus growth-regulating agents or plant protection active ingredients, it is preferred that the plant or fungus growth-regulating agents or plant protection agents can be delivered via a controlled by the carrier period. A further contribution to solving above-mentioned objects provides the use of hollow bodies having a shell of an inorganic or organic material for the production of water-absorbing polymeric formations. Into diesel sem context particularly preferred to use those hollow bodies which have already been mentioned above in connection with the inventive water-absorbing polymer structures as a preferred hollow body.

The invention will now be described with reference to figures, test methods and non limitieren- the examples.

TEST METHODS

Determining the absorption rate

The determination of the absorption speed was carried out by measuring the so-called "Free Swell Rate - FSR" in accordance with the process described in EP-AO 443 627 on the side 12 tests.

Determination of absorption under pressure

As, ^ 4AP "Marked absorption against a pressure of 0.7 psi (about 50 g / cm 2) is determined according to the ERT 442.2-02, where" ERT "for" EDANA recommended test "and" EDANA "for, £ , is uropean Disposables and nonwovens Association ".

Determination of Retention

The designated as "CRC" retention is determined according to the ERT 441.2-02. Determination of the permeability

The permeability was carried out by the measurement of the so-called Saline Flow Conductivity - SFC according to the process described in WO-A-95/26209 test procedure.

EXAMPLES

Comparative example

A monomer solution consisting of 320 g acrylic acid, 248.649 g NaOH (50%), 407.022 g of deionized water, 0.631 g of polyethylene glycol 300 diacrylate (with a content of active substance of 76.1 wt .-%) and 1.31 g polyethylene glycol-500-O-monoallyletheracrylat (with a content of active substance of 73.1 wt .-%) was deoxygenated by purging with nitrogen to remove dissolved oxygen and cooled to the start temperature of 4 ° C. After reaching the starting temperature of the initiator solution (0.3 g of sodium peroxydisulphate in 10.0 g H 2 O, 0.07 g of 35% hydrogen peroxide solution in 10.0 g H 2 O and 0.015 g ascorbic acid in 2, 0 g H 2 O) was added. After the final temperature of about 110 0 C was reached, the resulting gel was crushed with a meat grinder and dried for 2 hours at 150 0 C in a drying cabinet. The dried polymer was coarsely crushed, ground by means of a cutting mill SM 100 with a 2 mm sieve and sieved to a powder with a particle size 150-710 microns (= powder A).

The powder A was mixed with an aqueous solution consisting of ethylene carbonate (1 wt .-% based on the powder A) (0.3 wt .-% based on the powder A) (0.3 based, aluminum sulfate wt .-%, aluminum lactate (on the powder a) and water 3 wt .-% to the powder a) in a laboratory mixer and then in the furnace for 90 min. heated at 170 0 C (= not erfmdungsgemä- SLI powder A).

example 1

Comparative Example 1 except that the monomer solution to, is added 0.25 wt .-% (based on the total weight of monomer) EXPANCEL ® 930 DU 120 particles which wur- predispersed in 50 ml of water is repeated. Obtained powder B of the invention.

example 2

Comparative Example 1 except that the monomer solution 0.5 wt .-% (based on the total weight of monomer) is EXPANCEL ® 930 DU 120 particles which were pre-dispersed in 50 ml of water added is repeated. Obtained powder C according to the invention.

example 3

Comparative Example 1 except that the monomer solution 0.5 wt .-% (based on the total weight of monomer) is EXPANCEL ® 091 WU 80 particles, which were pre-dispersed in 50 ml of water added is repeated. Obtained powder D of the present invention.

The powder obtained above A to D were characterized by the following properties:

Figure imgf000037_0001

The results of the above table shows that the absorption rate (FSR value) can be significantly improved by the use of Expancel "particles, without the other absorption properties (AAPojpsi, CRC and SFC) is decisively deteriorated.

Claims

1. Water-absorbing polymeric formations, comprising at least partially hollow body having a shell of an inorganic or organic
Material.
2. The water-absorbent polymer structure according to claim 1, wherein the water-absorbing polymeric formations based on partially neutralized, cross-linker acrylic acid.
3, water-absorbing polymer structure is embedded The water-absorbing polymer structure according to claim 1 or 2, wherein at least a portion formed of the hollow body in the as a matrix.
4. The water-absorbent polymer structure according to one of the preceding claims, wherein the hollow body are evenly distributed in the water-absorbing polymeric formations.
5. The water-absorbent polymer structure according to one of the preceding claims, wherein the water-absorbing polymeric formations include the hollow body in an amount in a range of 0.001 to 15 wt .-%, based on the total weight of the water-absorbent polymer structure.
6. The water-absorbent polymer structure according to one of the preceding claims, wherein the water-absorbent polymer structure is obtainable by a process comprising the process steps: i) radical polymerization of an aqueous monomer solution comprising a polymerizable, monoethylenically unsaturated, acid group-bearing monomer (αl) or a salt thereof , optionally one with the monomer (αl) polymerizable mo- noethylenisch unsaturated monomer (α2), and optionally a crosslinker (α3) to obtain a polymer gel; ii) optionally, comminuting the hydrogel; iii) drying the optionally comminuted hydrogel to obtain water-absorbing polymeric particles; iv) optionally grinding and sieving the thus obtained water-absorbing polymer particles; v) optionally, further surface modification of the thus obtained water-absorbing polymer particles; wherein at least one of the conditions is satisfied I) and II): I) the hollow body having a shell of an inorganic or organic material can be added to the monomers in process step i);
II) the hollow body having a shell of an inorganic or organic material can be obtained in the hydrogel in method step i) or incorporated in the product obtained in method step ii), crushed hydro gel.
7. The water-absorbent polymer structure according to one of the preceding claims, wherein the organic material is a polymeric thermo-plastic material which encloses a propellant.
8. The water-absorbent polymer structure according to claim 7, wherein the hollow bodies are in the form of particles which have an average Volume determination men and 2 Vi> Vi can be expanded by increasing the temperature to the average volume V.
9. The water-absorbent polymer structure according to claim 8, wherein the expansion of the particles takes place during at least one of the method steps i) to v).
10. The water-absorbent polymer structure according to claim 7, wherein the hollow bodies are in the form of particles which have an average Volume determination men V 2 have and which are obtainable in that the particles from an average volume Vi <V 2 on the average volume V have been expanded. 2
11. The water-absorbent polymer structure according to one of claims 1 to 6, wob the polymeric material is a polymeric egg, non-thermoplastic material.
12. The water-absorbent polymer structure according to one of claims 1 to 7, wherein the inorganic material is a polycrystalline aluminum oxide.
13. The water-absorbent polymer structure according to one of the preceding claims, wherein said one test method described herein specific absorption rate comprise at least 0.3 g / g / sec.
14. The water-absorbent polymer structure according to one of the preceding claims, wherein said said at least one of the following properties: (SSL) an described herein in accordance with the test method specified absorption under a pressure of 50 g / cm 2 of at least 22.0 g / g;
(SS2) according to the herein described a test method specified retention of at least 26 g / g; (SS3) a test method described herein certain permeability of at least 45 x 10 "7 cm 3 sec / g.
15. A process for producing water-absorbing polymeric formations, comprising the steps of: i) radical polymerization of an aqueous monomer solution comprising a polymerizable, monoethylenically unsaturated, acid group-bearing monomer (αl) or a salt thereof, optionally one (with the monomer αl) polymerizable monoethylenically unsaturated monomer (α2), and optionally a crosslinker (α3) to obtain a polymer gel; ii) optionally, comminuting the hydrogel; iii) drying the optionally comminuted hydrogel to obtain water-absorbing polymeric particles; iv) optionally grinding and sieving the thus obtained water absorbent polymer particles; v) optionally, further surface modification of the thus obtained water-absorbing polymer particles; wherein at least one of the conditions I) and II) is satisfied:
I) a hollow body with a shell of an inorganic or organic material see to be added to the monomers in process step i);
II) a hollow body with a shell of an inorganic or organic material may be incorporated in the product obtained in process step i) or in the hydrogel obtained in step ii), crushed hydro gel.
16. The method of claim 15, wherein the organic material is a polymeric thermoplastic material which encloses a blowing agent, and wherein the hollow body in the form of particles having a mean volume Vi and by raising the temperature to the average volume V 2> Vi can be expanded.
17. The method of claim 16, wherein the expansion of the particles takes place during at least one of the method steps i) to v).
18. The method of claim 14, wherein the organic material is a polymeric thermoplastic material which encloses a blowing agent, and wherein the hollow body in the form of particles having an average volume V 2 and which are obtainable in that the particles have been expanded, starting from a mean volume Vi <V 2 on the mean volume V2.
19. The method of claim 15, wherein the polymeric material is a polymeric, non-thermoplastic material.
20. The method of claim 15, wherein the inorganic material is a polycrystalline alumina.
21. Water-absorbent polymer structure, obtainable by the process according to any one of claims 15 to 20th
22. The water-absorbent polymer structure according to claim 21, wherein said one test method described herein specific absorption rate comprise at least 0.3 g / g / sec.
23. The water-absorbent polymer structure according to claim 21 or 22, wherein said said at least one of the following properties: (SSL) an described herein in accordance with the test method specified absorption under a pressure of 50 g / cm 2 of at least 22.0 g / g; (SS2) according to the herein described a test method specified re- tention of at least 26 g / g;
(SS3) a test method described herein certain permeability of at least 45 x 10 "7 g / cm 3 sec / g.
24. A composite comprising water-absorbent polymer structure according to any one of claims 1 to 13 or 21 to 23 and a substrate.
25. A method for producing a composite, wherein water-absorbing polymer structure according to one of claims 1 to 14 or 21 to 23 and a substrate and optionally an additive are brought in con- tact with each other.
26. A composite obtainable by a process according to claim 25th
27. Foams, formed bodies, fibers, sheets, films, cables, sealing materials, liquid-absorbing hygiene articles, carriers for plant and fungus growth-regulating agents, packaging materials, soil additives or building materials, comprising water-absorbing polymeric formations according to any one of claims 1 to 14 or 21 to 23 or the composite of claim 24 or 26th
28. Use of the water-absorbent polymer structure according to any one of claims 1 to 14 or 21 to 23 or the composite of claim 24 or 26 in foams, formed bodies, fibers, sheets, films, cables, sealing materials, liquid-absorbing hygiene articles, carriers for plant and fungus growth-regulating agents , packaging materials, soil additives, for the controlled release of active ingredients or in construction materials.
29. The use of hollow bodies having a shell of an inorganic or organic materials for producing water-absorbing polymeric formations.
PCT/EP2010/052931 2009-04-07 2010-03-09 Use of hollow bodies for producing water-absorbent polymer structures WO2010115671A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE102009016404A DE102009016404A1 (en) 2009-04-07 2009-04-07 Use of hollow bodies for producing water-absorbing polymer structure
DE102009016404.9 2009-04-07

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US13/201,780 US20120001122A1 (en) 2009-04-07 2010-03-09 Use of hollow bodies for producing water-absorbing polymer structures
CN2010800131629A CN102361653A (en) 2009-04-07 2010-03-09 Use of hollow bodies for producing water-absorbent polymer structures
JP2012503940A JP2012522880A (en) 2009-04-07 2010-03-09 Use of hollow bodies for the production of water-absorbing polymers
EP10707284A EP2416810A1 (en) 2009-04-07 2010-03-09 Use of hollow bodies for producing water-absorbent polymer structures

Publications (1)

Publication Number Publication Date
WO2010115671A1 true WO2010115671A1 (en) 2010-10-14

Family

ID=42154533

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/052931 WO2010115671A1 (en) 2009-04-07 2010-03-09 Use of hollow bodies for producing water-absorbent polymer structures

Country Status (8)

Country Link
US (1) US20120001122A1 (en)
EP (1) EP2416810A1 (en)
JP (1) JP2012522880A (en)
KR (1) KR20120043165A (en)
CN (1) CN102361653A (en)
DE (1) DE102009016404A1 (en)
TW (1) TW201036699A (en)
WO (1) WO2010115671A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011136301A1 (en) 2010-04-27 2011-11-03 株式会社日本触媒 Method for producing polyacrylic acid (salt)-based water absorbent resin powder
EP2583697A1 (en) * 2011-10-21 2013-04-24 The Procter and Gamble Company Absorbent core
DE102011086522A1 (en) 2011-11-17 2013-05-23 Evonik Degussa Gmbh Superabsorbent polymers for highly filled or fiber hygiene products
EP2699609B1 (en) 2011-04-20 2017-10-18 Evonik Degussa GmbH Process for producing water-absorbing polymers with high absorption rate
US10196330B2 (en) 2013-10-09 2019-02-05 Protia As Process for dehydroaromatization of alkanes with in-situ hydrogen removal

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007121937A2 (en) 2006-04-21 2007-11-01 Evonik Stockhausen Gmbh Surface post-cross-linked superabsorber treated with aluminium lactate and optionally aluminium sulphate
US8357766B2 (en) 2008-10-08 2013-01-22 Evonik Stockhausen Gmbh Continuous process for the production of a superabsorbent polymer
DE102009028156A1 (en) 2009-07-31 2011-02-03 Evonik Stockhausen Gmbh Whippable o / w emulsion
EP2371869A1 (en) 2010-03-30 2011-10-05 Evonik Stockhausen GmbH A process for the production of a superabsorbent polymer
DE102010043113A1 (en) 2010-10-29 2012-05-03 Evonik Stockhausen Gmbh A process for the preparation of improved absorbent polymers by means of cryogenic grinding
DE102011004815A1 (en) 2011-02-28 2012-08-30 Evonik Stockhausen Gmbh Skin and hand cleansing compositions containing superabsorbent particles
US8987545B2 (en) * 2011-05-18 2015-03-24 The Procter & Gamble Company Feminine hygiene absorbent articles comprising water-absorbing polymer particles
DE102011086516A1 (en) 2011-11-17 2013-05-23 Evonik Degussa Gmbh Superabsorbent polymers with rapid absorption properties as well as methods for the preparation thereof
CN104114591B (en) 2012-02-15 2016-10-12 巴斯夫欧洲公司 Water-absorbing polymer particles have a high swelling ratio and high permeability
US9738769B2 (en) 2012-02-15 2017-08-22 Basf Se Water-absorbing polymer particles with high free swell rate and high permeability
ES2607441T3 (en) 2012-03-15 2017-03-31 Xtract Gmbh Procedure for the granulation of particulate material obtained from industrial processes, the granulate thus produced
DE102012102473A1 (en) 2012-03-22 2013-09-26 Xtract Gmbh Treating sewage sludge, useful for improving its storage- and/or transport properties, comprises mechanically dewatering sludge, and mixing dewatered sludge with superabsorbent or hydrogel to obtain granules with specific moisture content
EP2912110B1 (en) 2012-10-24 2018-12-05 Evonik Degussa GmbH Scent- and colour-stable water-absorbing composition
US9302248B2 (en) 2013-04-10 2016-04-05 Evonik Corporation Particulate superabsorbent polymer composition having improved stability
KR20180001245A (en) * 2016-06-27 2018-01-04 주식회사 엘지화학 Preparation method of super absorbent polymer, and super absorbent polymer
KR20180001243A (en) * 2016-06-27 2018-01-04 주식회사 엘지화학 Preparation method of super absorbent polymer, and super absorbent polymer
KR20190026355A (en) * 2017-09-05 2019-03-13 주식회사 엘지화학 Super absorbent polymer
KR20190026354A (en) * 2017-09-05 2019-03-13 주식회사 엘지화학 Super absorbent polymer

Citations (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1024195A (en) 1962-01-19 1966-03-30 Basf Ag Production of finely divided expandable thermoplastics
US3615972A (en) 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US3945956A (en) 1975-06-23 1976-03-23 The Dow Chemical Company Polymerization of styrene acrylonitrile expandable microspheres
DE2612846A1 (en) 1975-03-27 1976-10-07 Sanyo Chemical Ind Ltd A process for producing water absorbing resin
DE2706135A1 (en) 1977-02-14 1978-08-17 Stockhausen & Cie Chem Fab Thickener for retired intestinal contents and urinary
DE2840010A1 (en) 1977-12-15 1979-06-21 Nat Starch Chem Corp Graft copolymers and process for their preparation
US4286082A (en) 1979-04-06 1981-08-25 Nippon Shokubai Kagaku Kogyo & Co., Ltd. Absorbent resin composition and process for producing same
US4287308A (en) 1980-02-14 1981-09-01 Matsumoto Yushi-Seiyaku Co., Ltd. Process for preparing a thermo-expandable microspheres
US4340706A (en) 1980-03-19 1982-07-20 Seitetsu Kagaku Co., Ltd. Alkali metal acrylate or ammonium acrylate polymer excellent in salt solution-absorbency and process for producing same
DE3503458A1 (en) 1984-02-04 1985-08-08 Arakawa Chem Ind A process for producing improved water-absorbent resins
JPS62286534A (en) 1986-06-04 1987-12-12 Matsumoto Yushi Seiyaku Kk Manufacture of thermal expansion microcapsule
DE3713601A1 (en) 1987-04-23 1988-11-10 Stockhausen Chem Fab Gmbh A process for producing a highly water absorbent polymer
EP0443627A2 (en) 1990-02-23 1991-08-28 Kimberly-Clark Corporation Absorbent structure
DE4020780C1 (en) 1990-06-29 1991-08-29 Chemische Fabrik Stockhausen Gmbh, 4150 Krefeld, De
EP0486080A2 (en) 1990-11-12 1992-05-20 Casco Nobel Ab Expandable thermoplastic microspheres and a method for the production and use thereof
US5118719A (en) 1991-10-22 1992-06-02 Nalco Chemical Company Enhancing absorption rates of superabsorbents by incorporating a blowing agent
US5145713A (en) 1990-12-21 1992-09-08 Bell Communications Research, Inc. Stoichiometric growth of compounds with volatile components
DE4244548A1 (en) 1992-12-30 1994-07-07 Stockhausen Chem Fab Gmbh Powdered absorbent under load aqueous liquids as well as blood polymers, processes for their preparation and their use in textile constructions for the body hygiene
DE4418818A1 (en) 1993-07-09 1995-01-12 Stockhausen Chem Fab Gmbh Powdered, crosslinked, aqueous liquids and body fluids absorbent polymers, processes for their preparation and their use
US5399391A (en) 1993-08-20 1995-03-21 Perez-Viera; Margarita Instant christmas dress-up
DE4333056A1 (en) 1993-09-29 1995-03-30 Stockhausen Chem Fab Gmbh Powdery, aqueous fluid absorbent polymers, processes for their preparation and their use as absorbents
WO1995026209A1 (en) 1994-03-29 1995-10-05 The Procter & Gamble Company Absorbent members for body fluids having good wet integrity and relatively high concentrations of hydrogel-forming absorbent polymer
WO1996005234A1 (en) 1994-08-12 1996-02-22 Kao Corporation Process for producing improved super absorbent polymer
US5536756A (en) 1992-04-15 1996-07-16 Matsumoto Yushi-Seiyaku Co., Ltd. Thermoexpandable microcapsule and production
DE19529348A1 (en) 1995-08-09 1997-02-13 Stockhausen Chem Fab Gmbh Absorbents for water and aqueous liquids, as well as processes for their preparation and use
WO1999034843A1 (en) 1998-01-07 1999-07-15 The Procter & Gamble Company Absorbent polymer compositions having high sorption capacities under an applied pressure
US6235800B1 (en) 1998-03-13 2001-05-22 Matsumoto Yushi-Seiyaku Co., Ltd. Heat-expandable microcapsules and method of utilizing the same
US6235394B1 (en) 1998-02-24 2001-05-22 Matsumoto Yushi-Seiyaku Co., Ltd. Heat-expandable microcapsules, process for producing the same, and method of utilizing the same
US6284362B1 (en) * 1997-07-18 2001-09-04 Sanyo Chemical Industries, Ltd. Absorbent compositions, methods for producing thereof and absorbent products
WO2002056812A2 (en) 2000-12-20 2002-07-25 Kimberly-Clark Worldwide, Inc. Thin, high capacity multi-layer absorbent core
US6509384B2 (en) 2000-04-28 2003-01-21 Akzo Nobel N.V. Chemical product and method
EP1288272A1 (en) 2000-04-28 2003-03-05 Kureha Kagaku Kogyo Kabushiki Kaisha Heat-expandable macrosphere and process for producing the same
WO2004037903A2 (en) 2002-10-25 2004-05-06 Stockhausen Gmbh Absorbent polymer structure provided with an improved retention capacity and permeability
WO2004072160A1 (en) 2003-02-11 2004-08-26 Akzo Nobel N.V. Microspheres
US20040176486A1 (en) 2001-05-25 2004-09-09 Joey Glorioso Foam insulation made with expandable microspheres and methods
WO2004080498A1 (en) * 2003-03-12 2004-09-23 3M Innovative Properties Company Absorbent polymer compositions, medical articles, and methods
US20050137546A1 (en) * 2003-12-19 2005-06-23 Joy Mark C. Superabsorbent polymer having increased rate of water absorption
JP2005213379A (en) 2004-01-29 2005-08-11 Sanyo Chem Ind Ltd Thermally expandable microcapsule
JP2005272633A (en) 2004-03-24 2005-10-06 Sanyo Chem Ind Ltd Hollow resin particle and thermally expandable microcapsule
EP1757639A2 (en) 2005-08-22 2007-02-28 Rohm and Haas Company Methods for using hollow sphere polymers
WO2007091961A1 (en) 2006-02-10 2007-08-16 Akzo Nobel N.V. Microspheres
WO2007091960A1 (en) 2006-02-10 2007-08-16 Akzo Nobel N.V. Microspheres
WO2007142593A1 (en) 2006-06-08 2007-12-13 Akzo Nobel N.V. Microspheres
WO2008029428A1 (en) * 2006-09-06 2008-03-13 Fintex & Partners Italia S.P.A. Absorbent web product, method of obtaining it and absorbent article utilizing this product

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0688074A (en) * 1992-09-08 1994-03-29 Hitachi Chem Co Ltd Soil conditioner
AT240363T (en) * 1996-08-23 2003-05-15 Stockhausen Chem Fab Gmbh Carrier with superabsorbent material, process for their preparation and use
WO1999003577A1 (en) * 1997-07-18 1999-01-28 Sanyo Chemical Industries, Ltd. Absorbent composition, process for producing the same, and absorbent article
DE102006060156A1 (en) * 2006-12-18 2008-06-19 Evonik Stockhausen Gmbh Absorbing polymer structure, which were prepared using the polymer dispersions
CN102292362A (en) * 2008-11-21 2011-12-21 巴斯夫欧洲公司 A method for preparing permeable absorbent polymer particles by polymerizing droplets of a monomer solution

Patent Citations (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1024195A (en) 1962-01-19 1966-03-30 Basf Ag Production of finely divided expandable thermoplastics
US3615972A (en) 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
DE2612846A1 (en) 1975-03-27 1976-10-07 Sanyo Chemical Ind Ltd A process for producing water absorbing resin
US4076663A (en) 1975-03-27 1978-02-28 Sanyo Chemical Industries, Ltd. Water absorbing starch resins
US3945956A (en) 1975-06-23 1976-03-23 The Dow Chemical Company Polymerization of styrene acrylonitrile expandable microspheres
DE2706135A1 (en) 1977-02-14 1978-08-17 Stockhausen & Cie Chem Fab Thickener for retired intestinal contents and urinary
DE2840010A1 (en) 1977-12-15 1979-06-21 Nat Starch Chem Corp Graft copolymers and process for their preparation
US4286082A (en) 1979-04-06 1981-08-25 Nippon Shokubai Kagaku Kogyo & Co., Ltd. Absorbent resin composition and process for producing same
US4287308A (en) 1980-02-14 1981-09-01 Matsumoto Yushi-Seiyaku Co., Ltd. Process for preparing a thermo-expandable microspheres
US4340706A (en) 1980-03-19 1982-07-20 Seitetsu Kagaku Co., Ltd. Alkali metal acrylate or ammonium acrylate polymer excellent in salt solution-absorbency and process for producing same
DE3503458A1 (en) 1984-02-04 1985-08-08 Arakawa Chem Ind A process for producing improved water-absorbent resins
JPS62286534A (en) 1986-06-04 1987-12-12 Matsumoto Yushi Seiyaku Kk Manufacture of thermal expansion microcapsule
DE3713601A1 (en) 1987-04-23 1988-11-10 Stockhausen Chem Fab Gmbh A process for producing a highly water absorbent polymer
EP0443627A2 (en) 1990-02-23 1991-08-28 Kimberly-Clark Corporation Absorbent structure
DE4020780C1 (en) 1990-06-29 1991-08-29 Chemische Fabrik Stockhausen Gmbh, 4150 Krefeld, De
EP0486080A2 (en) 1990-11-12 1992-05-20 Casco Nobel Ab Expandable thermoplastic microspheres and a method for the production and use thereof
US5145713A (en) 1990-12-21 1992-09-08 Bell Communications Research, Inc. Stoichiometric growth of compounds with volatile components
US5118719A (en) 1991-10-22 1992-06-02 Nalco Chemical Company Enhancing absorption rates of superabsorbents by incorporating a blowing agent
US5536756A (en) 1992-04-15 1996-07-16 Matsumoto Yushi-Seiyaku Co., Ltd. Thermoexpandable microcapsule and production
DE4244548A1 (en) 1992-12-30 1994-07-07 Stockhausen Chem Fab Gmbh Powdered absorbent under load aqueous liquids as well as blood polymers, processes for their preparation and their use in textile constructions for the body hygiene
DE4418818A1 (en) 1993-07-09 1995-01-12 Stockhausen Chem Fab Gmbh Powdered, crosslinked, aqueous liquids and body fluids absorbent polymers, processes for their preparation and their use
US5399391A (en) 1993-08-20 1995-03-21 Perez-Viera; Margarita Instant christmas dress-up
DE4333056A1 (en) 1993-09-29 1995-03-30 Stockhausen Chem Fab Gmbh Powdery, aqueous fluid absorbent polymers, processes for their preparation and their use as absorbents
WO1995026209A1 (en) 1994-03-29 1995-10-05 The Procter & Gamble Company Absorbent members for body fluids having good wet integrity and relatively high concentrations of hydrogel-forming absorbent polymer
WO1996005234A1 (en) 1994-08-12 1996-02-22 Kao Corporation Process for producing improved super absorbent polymer
DE19529348A1 (en) 1995-08-09 1997-02-13 Stockhausen Chem Fab Gmbh Absorbents for water and aqueous liquids, as well as processes for their preparation and use
US6284362B1 (en) * 1997-07-18 2001-09-04 Sanyo Chemical Industries, Ltd. Absorbent compositions, methods for producing thereof and absorbent products
WO1999034843A1 (en) 1998-01-07 1999-07-15 The Procter & Gamble Company Absorbent polymer compositions having high sorption capacities under an applied pressure
US6235394B1 (en) 1998-02-24 2001-05-22 Matsumoto Yushi-Seiyaku Co., Ltd. Heat-expandable microcapsules, process for producing the same, and method of utilizing the same
US6235800B1 (en) 1998-03-13 2001-05-22 Matsumoto Yushi-Seiyaku Co., Ltd. Heat-expandable microcapsules and method of utilizing the same
US6509384B2 (en) 2000-04-28 2003-01-21 Akzo Nobel N.V. Chemical product and method
EP1288272A1 (en) 2000-04-28 2003-03-05 Kureha Kagaku Kogyo Kabushiki Kaisha Heat-expandable macrosphere and process for producing the same
WO2002056812A2 (en) 2000-12-20 2002-07-25 Kimberly-Clark Worldwide, Inc. Thin, high capacity multi-layer absorbent core
US20050079352A1 (en) 2001-05-25 2005-04-14 Joey Glorioso Expandable microspheres for foam insulation and methods
US20040176486A1 (en) 2001-05-25 2004-09-09 Joey Glorioso Foam insulation made with expandable microspheres and methods
WO2004037903A2 (en) 2002-10-25 2004-05-06 Stockhausen Gmbh Absorbent polymer structure provided with an improved retention capacity and permeability
WO2004072160A1 (en) 2003-02-11 2004-08-26 Akzo Nobel N.V. Microspheres
WO2004080498A1 (en) * 2003-03-12 2004-09-23 3M Innovative Properties Company Absorbent polymer compositions, medical articles, and methods
US20050137546A1 (en) * 2003-12-19 2005-06-23 Joy Mark C. Superabsorbent polymer having increased rate of water absorption
JP2005213379A (en) 2004-01-29 2005-08-11 Sanyo Chem Ind Ltd Thermally expandable microcapsule
JP2005272633A (en) 2004-03-24 2005-10-06 Sanyo Chem Ind Ltd Hollow resin particle and thermally expandable microcapsule
EP1757639A2 (en) 2005-08-22 2007-02-28 Rohm and Haas Company Methods for using hollow sphere polymers
WO2007091961A1 (en) 2006-02-10 2007-08-16 Akzo Nobel N.V. Microspheres
WO2007091960A1 (en) 2006-02-10 2007-08-16 Akzo Nobel N.V. Microspheres
WO2007142593A1 (en) 2006-06-08 2007-12-13 Akzo Nobel N.V. Microspheres
WO2008029428A1 (en) * 2006-09-06 2008-03-13 Fintex & Partners Italia S.P.A. Absorbent web product, method of obtaining it and absorbent article utilizing this product

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Modern Superabsorbent Polymer Technology", 1998, WILEY-VCH
CAVALIERI ET AL.: "Stable Polymeric Microballons as Multifunctional Device for Biomedical Uses: Synthesis and Characterization", LANGMUIR, vol. 21, no. 19, 2005, pages 8.758 - 8.764, XP002526229
HEUVINGH ET AL.: "Salt softening ofpolyelectrolyte multilayer capsules", LANGMUIR, vol. 21, no. 7, 2005, pages 3.165 - 3.171

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011136301A1 (en) 2010-04-27 2011-11-03 株式会社日本触媒 Method for producing polyacrylic acid (salt)-based water absorbent resin powder
EP2699609B1 (en) 2011-04-20 2017-10-18 Evonik Degussa GmbH Process for producing water-absorbing polymers with high absorption rate
EP2583697A1 (en) * 2011-10-21 2013-04-24 The Procter and Gamble Company Absorbent core
WO2013059421A1 (en) * 2011-10-21 2013-04-25 The Procter & Gamble Company Absorbent core
DE102011086522A1 (en) 2011-11-17 2013-05-23 Evonik Degussa Gmbh Superabsorbent polymers for highly filled or fiber hygiene products
US20140257223A1 (en) * 2011-11-17 2014-09-11 Evonik Degussa Gmbh Super-absorbing polymers with rapid absorption properties and method for producing the same
US10391195B2 (en) 2011-11-17 2019-08-27 Evonik Degussa Gmbh Super-absorbing polymers with rapid absorption properties and method for producing the same
US10196330B2 (en) 2013-10-09 2019-02-05 Protia As Process for dehydroaromatization of alkanes with in-situ hydrogen removal

Also Published As

Publication number Publication date
JP2012522880A (en) 2012-09-27
US20120001122A1 (en) 2012-01-05
DE102009016404A1 (en) 2010-10-21
TW201036699A (en) 2010-10-16
CN102361653A (en) 2012-02-22
KR20120043165A (en) 2012-05-03
EP2416810A1 (en) 2012-02-15

Similar Documents

Publication Publication Date Title
Omidian et al. Advances in superporous hydrogels
AU634872B2 (en) Method of treating the surface of an absorbent resin
CN100368464C (en) Water-absorbent resin having treated surface and process for producing the same
JP6093751B2 (en) Method for producing polyacrylic acid (salt) water absorbent resin powder and polyacrylic acid (salt) water absorbent resin powder
Po Water-absorbent polymers: a patent survey
JP4768688B2 (en) Water-absorbing foam-like crosslinked polymer
JP5647625B2 (en) Polyacrylic acid water-absorbing resin powder and method for producing the same
JP4991084B2 (en) Water absorbent, process for producing the same and use of the water absorbent
EP0882502B1 (en) Water-absorbent and process for preparing the same
EP1730218B1 (en) Particulate water absorbing agent with irregularly pulverized shape
ES2271690T3 (en) The water absorbent and process for its obtention.
US6136873A (en) Water-absorbing, expanded, crosslinked polymers, the production and use thereof
AU760448B2 (en) Powdery, cross-linked polymers which absorb aqueous liquids and blood, method for the production thereof and their use
US6849665B2 (en) Absorbent compositions
DE69927629T2 (en) A process for surface crosslinking of a water-absorbent resin
JP2011214016A (en) Water-absorbent resin, and method for producing the same and application
US20050048221A1 (en) Process for production of surface-treated particulate water-absorbent resin
US6620889B1 (en) Powdery, crosslinked absorbent polymers, method for the production thereof, and their use
JP5222721B2 (en) Water-absorbing polymer structure having high absorbency
CN100391548C (en) Water absorbent and preparation method of the same
EP1130045B1 (en) Process for producing a water-absorbent resin powder
CN101220159B (en) Water-absorbing polymer structures produced using polymer dispersions
JP5156234B2 (en) Hydrogels that absorb blood and / or body fluids
CN1277583C (en) Water-absorbing agent, its production method and sanitary material
JP2675729B2 (en) The method of producing a water-absorbent resin

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080013162.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10707284

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010707284

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2012503940

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 13201780

Country of ref document: US

NENP Non-entry into the national phase in:

Ref country code: DE

ENP Entry into the national phase in:

Ref document number: 20117026529

Country of ref document: KR

Kind code of ref document: A